JPH0432780B2 - - Google Patents
Info
- Publication number
- JPH0432780B2 JPH0432780B2 JP25780484A JP25780484A JPH0432780B2 JP H0432780 B2 JPH0432780 B2 JP H0432780B2 JP 25780484 A JP25780484 A JP 25780484A JP 25780484 A JP25780484 A JP 25780484A JP H0432780 B2 JPH0432780 B2 JP H0432780B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- melting
- soda
- lime glass
- color
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000011521 glass Substances 0.000 claims description 45
- 238000002844 melting Methods 0.000 claims description 26
- 230000008018 melting Effects 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 20
- 239000005361 soda-lime glass Substances 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000001603 reducing effect Effects 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 5
- 238000004040 coloring Methods 0.000 description 4
- 239000005308 flint glass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000006060 molten glass Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000005352 clarification Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018669 Mn—Co Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Glass Melting And Manufacturing (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は消色ソーダ石灰ガラスの製造方法の製
造方法に関する。更に詳述すれば、高い溶融性と
高い清澄性を有する消色されたソーダ石灰ガラス
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a decolorizing soda-lime glass. More specifically, the present invention relates to a method for producing bleached soda-lime glass having high meltability and high clarity.
(従来の技術)
溶融ガラスの消色に関する従来技術としては、
一般的なソーダ石灰ガラス殊に食卓用ガラス容器
或は包装用ガラス壜用として使用されるソーダ石
灰ガラスにおいて、その中に含まれる不都合な着
色成分例えばFe2+イオンの緑色を消色する場合、
Se−Co成分、Mn−Co成分を溶融前の原料バツ
チ中に添加し、溶融することにより、光学的補色
関係にある色を発色させて消色していた。或は
又、ガラスを強い酸化性条件下で溶融することに
より、緑着色性の強いFe2+イオンの含有比率を
低下せしめて、その着色を防止していた。(Conventional technology) Conventional technology regarding decolorization of molten glass is as follows.
In general soda lime glass, especially soda lime glass used for table glass containers or packaging glass bottles, when removing the green color of undesirable colored components such as Fe 2+ ions contained therein,
By adding the Se-Co component and the Mn-Co component to a raw material batch before melting and melting, colors that are optically complementary colors were developed and then discolored. Alternatively, by melting the glass under strongly oxidizing conditions, the content ratio of Fe 2+ ions, which have a strong green coloring property, is reduced, thereby preventing the glass from becoming colored.
従つて、従来技術では、フイーダー部でガラス
を消色するという技術的思想は全くなく、故に、
それに関する文献も全く存在しない。 Therefore, in the prior art, there is no technical concept of decolorizing the glass in the feeder section, and therefore,
There is no literature on it at all.
(発明が解決しようとする問題点)
省エネルギー化、省資源が叫ばれている今日、
当業界においても、ガラス溶融における溶融効率
の増大及び高効率な溶融ガラスの引き上げ量の増
大が強く望まれていた。(Problems that the invention aims to solve) Today, energy conservation and resource conservation are being called for.
In this industry as well, there has been a strong desire to increase the melting efficiency in glass melting and to increase the amount of molten glass pulled with high efficiency.
本発明者は、前記要望に答えるべく、鋭意研究
を重ねた結果、強い還元性の原料調合によつて得
られる、溶融能力、清澄能力が極めて高いソーダ
石灰ガラス(別名「FLAMBER GLASS」と称
し、以下“フランバーガラス”と記載する。)に
着目し、そして一方、そのガラスを単に食卓用ガ
ラス器或は包装用ガラス壜用等のガラス素材とし
ては、その還元性に起因する着色例えばFe2+イ
オンの緑色が製品品質を著しく低下させ或は製品
規格を大きく外していたので、殆ど見向きもされ
ていなかつたというその実態を鑑み、その欠点即
ち不都合な着色を有効に除去する特定の高マンガ
ン含有フリツトを一定の条件下で溶融混合し、有
効に消色することに成功した。 In order to meet the above-mentioned needs, the inventor of the present invention has conducted intensive research and has developed a soda-lime glass (also known as "FLAMBER GLASS") which has extremely high melting and clarification abilities and is obtained by blending strongly reducing raw materials. (hereinafter referred to as "Flambar glass"), and on the other hand, when using this glass simply as a glass material for table glassware or packaging glass bottles, coloring due to its reducibility, such as Fe 2 In view of the fact that the green color of + ions significantly degraded product quality or greatly exceeded the product specifications, it was hardly considered, so we developed a specific high manganese that effectively eliminates the drawback, that is, the inconvenient coloring. By melt-mixing the frits contained in the powder under certain conditions, we succeeded in effectively erasing the color.
本発明の目的は、溶融能力と清澄能力の高い強
還元性雰囲気で溶融される所謂“フランバーガラ
ス”を、殊に食卓用ガラス器或は包装用ガラス壜
用のガラス素材として使用する為に、その“フラ
ンバーガラス”特有の優れた溶融能力と清澄能力
とを維持しつつ、それ特有の不都合な着色を有効
に除去し、無色透明なソーダ石灰ガラスを大量に
溶融・製造し得る方法を提供することにある。 The purpose of the present invention is to use so-called "flamber glass", which is melted in a strongly reducing atmosphere with high melting ability and clarification ability, especially as a glass material for table glassware or packaging glass bottles. , a method for melting and manufacturing colorless and transparent soda-lime glass in large quantities by effectively removing the disadvantageous coloring characteristic of Flamber glass while maintaining its excellent melting ability and fining ability. It is about providing.
即ち、前記“フランバーガラス”において、高
い溶融性と清澄性を維持して、その特徴とする還
元性によつて生じる不都合な着色を有効に消去す
ることに成功したので、本出願として提案するも
のである。 That is, in the above-mentioned "Flambar glass", we have succeeded in maintaining high meltability and clarity and effectively eliminating the undesirable coloration caused by its characteristic reducing property, so we propose it as the present application. It is something.
(問題点を解決するための手段)
前記目的を効率よく達成するその技術的要旨
は、ガラス溶融窯のフイーダー部で、還元性で溶
融されたソーダ石灰ガラスの流量に対して、
SiO2 45〜60重量%
Na2O 15〜30 〃
MnO2 1〜38 〃
B2O3 0〜15 〃
を含有する高マンガン含有フリツトを、0.2〜10
%の重量比で添加し均一に溶融する点に存する。(Means for Solving the Problems) The technical gist for efficiently achieving the above objective is that in the feeder section of the glass melting furnace, SiO 2 45 ~ A high manganese-containing frit containing 60% by weight Na 2 O 15-30 〃 MnO 2 1-38 〃 B 2 O 3 0-15 〃 0.2-10
% by weight to ensure uniform melting.
更に詳述すれば、ソーダ石灰ガラス殊に高い溶
融性と高い清澄性を有する“フランバーガラス”
の溶融物に対して、特定された組成を有し、特定
の限定条件を有する高マンガン含有フリツトを比
較的短かいフイーダー部で、特定された一定の添
加量を添加することにより、所謂“フランバーガ
ラス”の特有の緑色を消去し、殆ど無色透明のソ
ーダ石灰ガラスを得るものである。 More specifically, soda-lime glass, especially "flamber glass", has high meltability and high clarity.
By adding a specified amount of high manganese-containing frit having a specified composition and specific limiting conditions to the melt of This method eliminates the characteristic green color of "bar glass" to obtain an almost colorless and transparent soda lime glass.
(作用)
食卓用ガラス器或は包装用ガラス壜を製造する
において、通常のソーダ石灰ガラス溶融手段で
は、その溶融能力から、その溶融ガラスを窯容量
の約0.5〜0.6倍/dayの割合でフイーダー部を流
すのが限界であつた。それ以上の流量において
は、充分に清澄されることなく、一部未溶解物が
流れることによつて、泡、石等がガラスに混入
し、欠陥あるガラスとなるからである。しかしな
がら、前記した如く、所謂“フランバーガラス”
においては、その溶融性・清澄性が優れているこ
とから、その窯容量の約0.8〜1.0倍/dayのガラ
ス流量を得ることが可能である。(Function) When manufacturing table glassware or packaging glass bottles, the molten glass is fed to a feeder at a rate of approximately 0.5 to 0.6 times the kiln capacity/day due to its melting ability with ordinary soda-lime glass melting means. There was a limit to what I could do. If the flow rate is higher than that, the glass will not be sufficiently clarified and some undissolved matter will flow, causing bubbles, stones, etc. to be mixed into the glass, resulting in defective glass. However, as mentioned above, so-called "flamber glass"
Because of its excellent melting and clarification properties, it is possible to obtain a glass flow rate of about 0.8 to 1.0 times the kiln capacity/day.
故に、そのガラス流量に添加される特定フリツ
トは、約4〜10メートルの比較的短かいフイーダ
ー長さで、前記“フランバーガラス”の比較的多
いガラス流量に対して、速やかに溶融して且つ均
質に混合し、そして、不都合な色を除去する能力
が必要とされる。その能力を有する特定フリツト
とは
SiO2 45〜60重量%
Na2O 15〜30 〃
MnO2 1〜38 〃
B2O3 0〜15 〃
を含有する高マンガン含有フリツトである。そし
て、その組成範囲内において、全マンガン中の
Mn3+の占める割合(以下、[Mn3+/総Mn]と記
す)が20%以上であることが望ましい、当該フリ
ツトを所謂“フランバーガラス”流に対して、
0.2〜10%の重量比で添加・溶融することによつ
て、刺激純度2.0%以下のほぼ無色透明なソーダ
石灰ガラスを得ることが出来る。尚、フイーダー
部でのガラス流に対しての、特定フリツトの添加
量は0.2%重量比未満の場合は、十分な消色が得
られず、10%重量比を越えるときは充分なフリツ
ト溶融のために逆に流出速度が制限される等の不
都合が生じる。従つて、特定されたその範囲が逸
脱されたときは、初期の目的の一つの効率的な消
色が達成され難くなる。 Therefore, the particular frit added to the glass flow rate must melt quickly and with a relatively short feeder length of about 4 to 10 meters, for the relatively high glass flow rate of the "Flambar glass". The ability to mix homogeneously and eliminate unwanted colors is required. A specific frit having this ability is a high manganese-containing frit containing 45-60% by weight of SiO2, 15-30% Na2O , 1-38% MnO2 , and 0-15 % B2O3. Within that composition range, the total amount of manganese is
It is desirable that the proportion of Mn 3+ (hereinafter referred to as [Mn 3+ /total Mn]) is 20% or more.
By adding and melting at a weight ratio of 0.2 to 10%, almost colorless and transparent soda lime glass with an irritation purity of 2.0% or less can be obtained. If the amount of specific frit added to the glass flow in the feeder section is less than 0.2% by weight, sufficient decolorization will not be obtained, and if it exceeds 10% by weight, sufficient frit melting will not be achieved. Therefore, disadvantages arise, such as the outflow rate being restricted. Therefore, when the specified range is deviated from, one of the initial objectives, efficient decolorization, becomes difficult to achieve.
前記マンガン含有フリツトはフイーダー部で溶
融した際、マンガン成分はマンガンイオン
(Mn2+、Mn3+)の状態で存在し、そのMn3+が溶
融ガラス中の鉄イオン(Fe2+)に作用し
Mn3++Fe2+→Mn2++Fe3+
の反応を起こして、Fe2+イオン色を消去し且つ
若干のMn3+イオンを微量残存して、吸収特性に
好都合に作用することにより、効率的な消色をな
すのである。 When the manganese-containing frit is melted in the feeder section, the manganese component exists in the state of manganese ions (Mn 2+ , Mn 3+ ), and the Mn 3+ acts on iron ions (Fe 2+ ) in the molten glass. By causing the reaction Mn 3+ + Fe 2+ → Mn 2+ + Fe 3+ to erase the Fe 2+ ion color and leaving a small amount of Mn 3+ ions, which favorably affects the absorption properties. This results in efficient color erasure.
(実施例)
次に本発明の実施例を記載し、本発明を更に詳
細に説明する。(Example) Next, Examples of the present invention will be described to explain the present invention in further detail.
容量約200トンのガラス溶融窯において、還元
性の強いソーダ石灰ガラスの原料バツチを溶融し
てなる、
SiO2 72.2重量%
Al2O3 2.2 〃
CaO 10.8 〃
MgO 0.2 〃
Na2O 12.5 〃
K2O 1.5 〃
Fe2O3 0.05 〃
その他 0.25 〃
の組成を有し、Fe2+/総Feの割合が約50%の関
係で溶融された“フランバーガラス”の、フイー
ダー部において約180トン/dayのガラス流量の
流れに対して、
SiO2 52.9重量%
Al2O3 1.4 〃
CaO 5.8 〃
B2O3 9.5 〃
Na2O 25.2 〃
MnO2 5.2 〃
の組成を有し、[Mn3+/総Mn]が42%である高
マンガン含有フリツトを2.5Kg/minの割合で添
加し(重量比=2%)、溶融した。 In a glass melting kiln with a capacity of about 200 tons, a raw material batch of highly reducing soda -lime glass is melted . Approximately 180 tons of "Flambar glass" having a composition of O 1.5 〃 Fe 2 O 3 0.05 〃 Other 0.25 〃 and melted with a Fe 2+ /total Fe ratio of approximately 50% was produced in the feeder section. It has a composition of SiO 2 52.9% by weight, Al 2 O 3 1.4 〃 CaO 5.8 〃 B 2 O 3 9.5 〃 Na 2 O 25.2 〃 MnO 2 5.2 〃, and [Mn 3+ / A high manganese-containing frit with a total Mn of 42% was added at a rate of 2.5 Kg/min (weight ratio = 2%) and melted.
それによつて、得られたガラスは、
主波長 −5260nm
刺激純度 0.4%
明 度 76.4%
(ガラス厚さ=20mm)
の色特性を有し、刺激純度0.4%の光学的特性を
有する殆ど無色透明なガラス製品を得ることがで
きた。尚、主波長の負記号(−)は補色主波長を
意味する。 Thereby, the obtained glass has color properties of dominant wavelength -5260 nm, excitation purity 0.4%, brightness 76.4% (glass thickness = 20 mm), and is almost colorless and transparent with optical properties of excitation purity 0.4%. I was able to obtain glass products. Note that the negative sign (-) of the dominant wavelength means the complementary dominant wavelength.
通常のフリントガラスと称されるソーダ石灰ガ
ラスの色特性は、概略、刺激純度2.0%以下、明
度75%以上(ガラス厚さ=20mm)の範囲内にあ
る。 The color characteristics of soda-lime glass, commonly called flint glass, are roughly within the range of irritation purity of 2.0% or less and brightness of 75% or more (glass thickness = 20 mm).
尚、本発明の比較例として、特定フリツトを添
加しないで得られた“フランバーガラス”の色特
性は
主波長 484.8nm
刺激純度 7.4%
明 度 76.2%
であつた。 As a comparative example of the present invention, the color characteristics of "Flambar glass" obtained without adding the specific frit were as follows: dominant wavelength: 484.8 nm, excitation purity: 7.4%, brightness: 76.2%.
更に第1図に示す如く、実施例のガラスの透過
率曲線はフリントガラスのそれに近く、無色透明
であつて、“フランバーガラス”のそれとは吸収
特性に大きな差を見出すことができる。 Further, as shown in FIG. 1, the transmittance curve of the glass of the example is close to that of flint glass, and is colorless and transparent, and there is a large difference in absorption characteristics from that of "Flambar glass."
そして、前記ガラス溶融窯における通常の溶融
手段での最大溶融能力は約120トン/dayであつ
たのに対して、本実施例においては、約1.5倍の
約180トン/dayを観測し、消色効率の高いのに
加え、溶融性及び清澄性向上が著しいという好結
果を得た。 While the maximum melting capacity of the glass melting furnace using normal melting means was approximately 120 tons/day, in this example, the maximum melting capacity was approximately 180 tons/day, which is approximately 1.5 times higher. In addition to high color efficiency, good results were obtained with remarkable improvements in meltability and clarity.
(発明の効果)
以上、本発明によつて、通常のソーダ石灰ガラ
スの溶融手段の溶融能力に比較し、約1.5倍強の
溶融性及び清澄性を得ることができ、そして、通
常のソーダ石灰ガラスの色調と変わりのない無色
透明のガラスを得ることができる。(Effects of the Invention) As described above, according to the present invention, it is possible to obtain meltability and clarity that are approximately 1.5 times higher than the melting ability of ordinary soda lime glass melting means, and It is possible to obtain colorless and transparent glass that has the same color tone as glass.
従つて、大量エネルギーを消費するガラス溶融
において、省エネルギー化が図り得たことは、当
業者のみならず、社会に対する貢献度は非常に大
なるものがある。 Therefore, the ability to save energy in glass melting, which consumes a large amount of energy, is a significant contribution not only to those skilled in the art but also to society.
第1図は、実施例、フリントガラス、“フラン
バーガラス”の各々の透過率曲線を示す。
1……実施例、2……フリントガラス、3……
“フランバーガラス”。
FIG. 1 shows the transmittance curves of the example, the flint glass, and the "flamber glass". 1... Example, 2... Flint glass, 3...
“Flambar glass”.
Claims (1)
融されたソーダ石灰ガラスの流量に対して、 SiO2 45〜60重量% Na2O 15〜30 〃 MnO2 1〜38 〃 B2O3 0〜15 〃 を含有する高マンガン含有フリツトを、0.2〜10
%の重量比で添加し溶融することを特徴とする消
色ソーダ石灰ガラスの製造方法。[Claims] 1. SiO 2 45-60% by weight Na 2 O 15-30 〃 MnO 2 1-38 〃 With respect to the flow rate of the soda lime glass melted in a reducing manner in the feeder section of the glass melting furnace. A high manganese-containing frit containing B 2 O 3 0-15
A method for producing decolorizing soda-lime glass, which is characterized by adding and melting at a weight ratio of %.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25780484A JPS61136924A (en) | 1984-12-06 | 1984-12-06 | Production of achromatic crown glass |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25780484A JPS61136924A (en) | 1984-12-06 | 1984-12-06 | Production of achromatic crown glass |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61136924A JPS61136924A (en) | 1986-06-24 |
JPH0432780B2 true JPH0432780B2 (en) | 1992-06-01 |
Family
ID=17311337
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP25780484A Granted JPS61136924A (en) | 1984-12-06 | 1984-12-06 | Production of achromatic crown glass |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61136924A (en) |
-
1984
- 1984-12-06 JP JP25780484A patent/JPS61136924A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS61136924A (en) | 1986-06-24 |
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